The present invention relates to multilayer transparent, antireflex, coloured or opaline, laminates having smooth or embossed surfaces, optionally thermomouldable with external layers of acrylic polymers, obtained by coextrusion or by compression molding or by casting, the laminates have anti-fragmentation properties and/or improved mechanical properties for use in building or in signs, in lighting, and in the medical field, etc.
In particular the invention relates to polymethylmethacrylate laminates with low thickness, in the range of 1.5 up to lower less than of 10 mm in thickness, preferably 2-5 mm.
The technical problem arises when a blunt instrument crashes into the panel or into the manufactured article obtained from the laminate the impact results in the formation of several fragments which cause undesired situations or of danger for whom and/or what lies under these structures.
Therefore an object of the present invention relates to panels/manufactured articles exhibiting superior antifragmentation properties and/or improved mechanical properties with respect to the crash.
The Applicant has unexpectedly and surprisingly found that it is possible to produce antifragmentation laminates based on acrylic polymers employing one or more polymeric continuous films which have an elastic modulus lower than that by PMMA of at least 30%, and/or elongation at break higher than at least 40, preferably of at least 60G measured by the test according to ISO 527 for laminates or films, or similar standards, placed inside the panel.
If only one film is utilized it can be placed about approximately in the middle of the panel, preferably it is placed closer to the tensile stress part during the impact (opposite surface to the surface subject to crash). In practice the film is placed preferably at a distance between 10 and 40% of the total thickness of the laminate with respect to the surface opposite to the surface subject to impact. It is also possible to produce the plate with two film insertions placed near both PMMA faces. According to a preferred embodiment of the invention additional films can also be inserted in the tensile stress part at distances generally of about 1 mm from each other.
The film has a thickness generally from 70 xcexcm up to 3 mm, preferably from 90 xcexcm to 2 mm. In the case of the preferred panels of the invention (2-5 mm), the film has a thickness comprised from 70 xcexcm to about 1.5 mm, preferably from 100 xcexcm to 1 mm.
The preferred polymers are transparent polyalkylenterephthalates with the alkyl of from 2 to 5 carbon atoms, for instance polyethylenterephthalate (PET), polybutylenterephthalate (PBT); polyvinylbutyral (PVB), transparent elastomers having an acrylic basis, transparent thermoplastic elastomers having a styrenic basis such as styrene/butadiene block copolymers, MBS type transparent copolymers having a styrenic basis, grafted polymers having a vinylic basis, such as maleic anhydride.
Polymeric films carried out by polymerization with ultraviolet light which comprise the following essential components:
(a) selected from the following components:
(a1) alkyl(meth)acrylate monomers having general formula: 
xe2x80x83wherein
R0xe2x80x2xe2x80x3 can be H, CH3 
R01 can be an alkyl from 1 to 10 carbon atoms, linear or branched when possible, preferably a linear alkylic chain, preferably from 1 to 6 carbon atoms, or a cycloalkyl alkyl from 5 to 15 carbon atoms, optionally containing heteroatoms, for instance cyclopenthyl or cyclohexyl;
(a2) aliphatic urethane oligomers di (tri) (meth)acrylates obtainable by reaction of a polyisocyanate, preferably di-tri-isocyanate having the general formula:
Rxe2x80x2xe2x80x94(NCO)q
xe2x80x83wherein Rxe2x80x2 is an aliphatic chain from 1 to 10 carbon atoms, preferably from 2 to 6, or an (alkyl)cycloaliphatic chain wherein the alkyl has the meaning described above and the cycloalkyl is a cyclic ring from 3 to 6 carbon atoms, preferably 5-6,
q being an integer from 2 to 6, preferably from 2 to 3, with
dialcohols of general formula:
HOxe2x80x94Rxe2x80x3xe2x80x94OH
xe2x80x83wherein Rxe2x80x3 has the same meaning as Rxe2x80x2; said prepolymer NCO or OH terminated is reacted with (meth)acrylic acid to obtain unsaturated terminations;
(a1) and (a2) can be also in admixture with each other, the amount of (a2) ranging from 20 to 80% by weight with respect to (a1), preferably between 20-40% by weight;
(b) selected from one or more of the following components:
(b1) polyalkylglycols di-poly-(meth)acrylates having the general formula: 
xe2x80x83wherein
R0 is equal to H, CH3 
Rxe2x80x2xe2x80x3 is equal to H, alkyl from 1 to 6 carbon atoms, preferably 1,
m is an integer from 2 to 12, preferably from 3 to 10;
(b2) alkyl di-poly-(meth)acrylates having the general formula: 
xe2x80x83wherein
R0 is equal to H, CH3,
nxe2x80x2 is an integer from 2 to 10, preferably from 4 to 6;
(b3) polyallylglycidylethers having the general formula: 
xe2x80x83wherein
nxe2x80x3 is an integer from 1 to 8, preferably from 3 to 6,
mxe2x80x2 is an integer from 2 to 10, preferably from 2 to 6,
R0xe2x80x2 is equal to H or an alkyl from 1 to 10 carbon atoms, preferably from 1 to 6;
the mixture of (a) and (b) is such as to have a viscosity from 50 to 3,000 cPoises, preferably from 100 to 1,000;
the component (b) can be omitted if in the formulation the component (a2) is present;
(c) hydroxy or carboxy alkyls alkyl(meth)acrylate from 2 to 6 carbon atoms, in amounts comprised between 0.5 and 5% by weight on the total, preferably 0.5-2, having the general formula: 
xe2x80x83wherein
R0 is H or CH3,
R02 is an alkyl from 1 to 10 carbon atoms, preferably from 1 to 6;
the amount of component (b) in the composition being comprised between 5 and 20% by weight, preferably between 5 and 10% by weight;
the film being obtained by UV polymerization in the presence of photoinitiators in amounts comprised between 1 and 10% by weight, preferably between 3 and 6% by weight;
the amount of (a) being the complement to 100.
The components of type (a2) are commercially known for instance as EB(copyright): such as EB 230, EB 264, EB 284, EB 244 produced by the company UCB.
The components of type (a1) are for instance methyl-, ethyl-, butyl-, isobutyl-, ethyl-hexyl acrylate, etc.
The compounds (b1) are also known commercially as: SARTOMER(copyright) 252, SARTOMER(copyright) 400, commercialized by Cray Valley, or tripropylenglycoldiacrylate (TPGDA); compounds (b2) are well known, hexandioldiacrylate (HDDA) can be mentioned; compounds (b3) are known in trade as SANTOLINK(copyright) XI 100 commercialized by Monsanto.
Compounds (c) which can be mentioned are hydroxyethyl- and hydroxypropyl-acrylates o-methacrylates; alpha-hydroxyethyl(meth)acrylate, carboxyethyl(meth)acrylate, for instance 2-carboxyethyl(meth)acrylate, are preferred.
These polymers can be used alone or in admixture with each other or with other polymers, for instance PMMA, MMA/-styrene in such ratios as to maintain the transparence and the elongation and modulus properties as defined above.
As polymerization photoinitiators of radical type, induced by ultraviolet light, one can those based on benzophenone such as ESACURE(copyright) KT 37 and UVECRYL(copyright) P115 by Lamberti, or such as IRGACURE(copyright) 500 by Ciba-Geigy. DAROCUR(copyright) 1173 and the other compounds disclosed in EP patent 374,516 can also be utilized; alkylic or aromatic peroxides and/or hydroperoxides, for instance benzene peroxide, ter-butylhydroperoxide, laurylperoxide, lauroylperoxide, cumylhydroperoxide, etc. can also be utilized. The amount of radicalic photoinitiators as said above ranges from 0.5 to 5% by weight, preferably from 0.5 to 2% by weight.
Panels having an acrylic basis containing antifragmentation polymers can be obtained by compression moulding, by casting, by coextrusion or by sizing.
The industrially preferred process for preparing the antifragmentation panels of the present invention is coextrusion utilizing a feed-block or optionally a head having separated channels. The usual procedures to eliminate and/or reduce the possible encapsulation and unstability phenomena at the interface among the various polymer layers are obviously to be carried out. Generally the thermal profiles of the extruders utilized for the various materials are such as to reduce the viscosity differences of the various polymeric melts, in the limits of the process conditions of the single materials. It is preferable degas to and dry the polymers before their use i.e. prior to an extrusion. In particular, in the case of the examples reported hereunder, the materials utilized have been dried with a stove under vacuum: for instance at 80xc2x0 C. for at least 16 hours for acrylic polymers and 60xc2x0 C. for 12 hours for styrene butadiene block copolymers. The utilized device for calendering is preferably a three cylinders device with independent motors.
Another process for producing the panels in question is by casting films polymerizable by UV described hereinunder.
Two PMMA (cast or extruded) laminates are taken and, are then superimposed and fixed to each other by overlapping at the borders of the laminates a biadhesive tape, for instance the product commercialized by 3M as VHB(copyright), having a thickness of some millimeters, in order to form an interspace of the same sizes of the laminates and thickness of the tape, taking care however of leaving one or more openings depending on the laminates size. This allows for the filling of the interspace with the UV polymerizable resin of the invention. The amount of resin is determined by considering besides the volume of the interspace also the dimensional shrinkage of the composition of the invention during the polymerization phase. The so obtained panel is inserted inside an oven equipped with UVA lamps and kept therein for the time necessary to achieved polymerization. Since this kind of lamps does not give rise to a strong increase of the temperature of the panel under preparation, the possible stresses of the panel, which could compromise the properties thereof, are thus avoided.
Crosslinking besides with the radicalic photoinitiators indicated above, can be also accomplished using mixed type radicalic and cationic photoinitiators. Polymerization and crosslinking cationic initiators with UV light are well known in the art, for instance triarylsulphonium salts, such as hexafluoroantimonates of triarylsulphonium (UVI-6974-CYRACURE(copyright), Union Carbide) and hexafluorophosphates of triarylsulphonium (UVI-6990-CYRACU-RE(copyright), Union Carbide), can be mentioned.
Such cationic photoinitiators are not inhibited by the oxygen and are employed in combination with radicalic photoinitiators preferably in a weight ratio between radicalic/cationic photoinitiator of at least 2/1, more preferably of 3/1. By employing such ratios it is possible to obtain the resin crosslinking in an air room with relative humidity of up to 60.
The cationic photoinitiator amount generally ranges from 0.01 to 3% by weight, preferably from 0.2 to 0.6.
Crosslinking with radicalic photoinitiators is generally carried out for times comprised between 30 sec-30 min depending on the lamp power, on the distance between panel and lamp, generally depending on the radiant power really reaching the panel to be polymerized.
The panels with the film according to the present invention can be resistant to an impact energy according to the test indicated in the examples.
Impact resistance is determined if the panel breaks without producing fragments, that is if fragments are retained by the film, or one merely determines the number of fragments of the panel. In the latter case, the panels of the invention when subjected to breaking forces give rise to an extremely limited number of fragments, generally of a few units, in practice they break into two fragments.
As elastomers having an acrylic basis, both homopolymers, for instance polybutyl(meth)acrylate and copolymers having also complex core-shell type structures, having one or more layers, similar to those generally used for impact-resistant PMMA, can be utilized.
As an example of elastomeric products having an acrylic basis see U.S. Pat. No. 5,183,851, U.S. Pat. No. 3,793,402, U.S. Pat. No. 3,808,180 and 4,180,529 incorporated herein by reference.
The films of the polymers utilized according to the present invention show a good adhesion with the acrylic polymers of the panels.
In case of poor adhesion it can be improved by using suitable bonding agents, transparent if the final composite must be transparent. For instance in case of PET and PBT, the bonding agents commercialized by the film suppliers are used. One can generally use bonding agents having an acrylic, butadiene, chloroprene, nitrilic, butyl, etc. basis, obviously selected on the basis of the chemical nature of the intermediate film.
For the elastomers having an acrylic or styrenic basis, the compatibility with PMMA is generally sufficient as such to assure a good adhesion.
For the films carried out via UV the product assuring the adhesion is already incorporated in the mixture to be polymerized (product C).
The polymers to obtain the films of the invention are well known in the art and in trade.
The preferred polymers are the polymers curable via UV as indicated above, the block styrene/butadiene copolymers. These latter are in trade as K RESIN by Phillips Petroleum.
Among the styrenic polymers, MBS terpolymer methylme-thacrylate-butadiene-styrene can also be mentioned.
With the preferred polymers uniform film with good adhesion to the acrylic basis is obtained, with the K resin bonding agents are not needed, for the reasons indicated above.
The panels with the film according to the present invention can be resistant to an impact energy according to the test described in the examples of multilayer plates obtained by the coextrusion technology indicated above.
Moreover accelerated ageing tests with QUVB lamps have shown that the inner layer of the film does not suffer ageing relative to the optical and mechanical properties even after 1000 hours of exposure or more. This is an advantage of the panels of the present invention since it is well known that films, for instance based on K-Resin as such, quickly age when exposed outside. This generally allows one to utilize films of the invention without requiring the use of a particular addition to increase the resistance to ageing. This brings process simplifications and leads also to a reduction in production costs.
Polymers having an acrylic basis according to the present invention are MMA homopolymers, MMA copolymers with other comonomers such as ethyl(meth)acrylate, butyl-(meth)acrylate in low concentrations. The amounts of comonomer are generally up to 10% by weight. MMA homopolymers or copolymers can be obtained by polymerization according to usual techniques, for instance by polymerization in mass or in suspension. The molecular weight can be adjusted by the addition of suitable chain transfer agents, for instance of the mercaptanes class. The weight average molecular weights Mw can generally be comprised in the range of 50,000-2,000,000.
The lowest values of molecular weight are preferred for the production of laminates by co(extrusion); the highest ones in case of preparation of laminates by casting.
One can also be used commercial impact-resistant PMMA, as an acrylic based polymer for the preparation of the external layers. Generally the impact-resistant PMMA contains an MMA homopolymer or copolymer as indicated above and in general from 20-50% by weight of an acrylic based elastomer, preferably having core-shell structures as indicated above for the films.
As examples of elastomeric products with an acrylic basis see for instance U.S. Pat. Nos. 5,183,851, U.S. Pat. No. 3,793,402, U.S. Pat. Nos. 3,808,180 and 4,180,529, herein incorporated for reference.